Patent GB-1399212-A (GB)
Title: Glasses and glass-ceramics and products made therefrom
IPC: C03C10/00
Filed: 1972-05-25
Abstract: 1399212 Glass ceramics; joining glass to glass OWENS-ILLINOIS Inc 25 May 1972 [25 May 1971 28 Feb 1972] 23738/74 Divided out of 1399211 Heading C1M A thermally crystallizable glass capable of being thermally in situ crystallized to a glassceramic which is thermally stable at temperatures of about 1500 F. for at least 1000 hours comprises 98-100% by weight of the following ingredients: 52-78À4% SiO 2 , 12À8-27À5% Al 2 O 3 , 2À4-7 Li 2 O, 0À25-6À7 ZnO, nucleating agent 3-9, the balance, if any, consisting of other compatible ingredients, each of said compatible ingredients consituting less than 1% by weight of the weight of the glass, said balance containing less than 0À1% by weight the weight out of the glass, wherein said nucleating agent is a mixture of TiO 2  and ZrO 2  and the ZrO 2  is present in an amount of 0À25-2À8% by weight, wherein the SiO 2 /Al 2 O 3  molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3  molar ratio is # 1, and (a) when the SiO 2 /Al 2 O 3  molar ratio is 4 or more but less than 5, the Li 2 O/Al 2 O 3  molar ratio is 0À55-0À91, and the ZnO/ Li 2 O molar ratio is 0À06-0À5; (b) when the SiO 2 /Al 2 O 3  molar ratio is 5-8 the Li 2 O/Al 2 O 3  molar ratio is 0À55-0À93, and the ZnO/Li 2 O molar ratio is 0À04- 0À5; and (c) when the SiO 2 /Al 2 O 3  molar ratio is from more than 8 and up to 9 the Li 2 O/Al 2 O 3  molar ratio is 0À8-0À93 and the ZnO/Li 2 O molar ratio is 0À04-0À5; and (d) the glass contains in weight per cent no more than 0À2 K 2 O or 0À2 Na 2 O or 0À2 (Na 2 O + K 2 O). The glass ceramic has a coefficient of linear thermal expansion of - 12 to +12 Î 10<SP>-7</SP> (0-700 C.). In examples additional ingredients given are 0À3% Sb 2 O 3  and 0À45 Fe 2 O 3 . Comparative examples include 0À1% Na 2 O + 0À20% K 2 O (10); 0À30% Na 2 O (23); 2À25% Li 2 O (24); 0À10% ZnO (27); and 0À30% F 2  (33). The glasses are formed into glass rods prior to heat-treatment for forming glass-ceramics. The rods are heated to their nucleating temperature (1350 F.) at 300 F. per hour and held at that temperature for 8 hours after which they are heated to the finishing temperature of 2100 or 2200 F. and held there for 2 hours. The rods were then cooled to 1500 F. at a rate of 25 F. per hour and then cooled to room temperature at the rate of about 300 F. per hour. A cellular matrix is formed of tubes of the glass ceramic fused together to provide a series of smooth-walled longitudinal passages the walls of which have an average coefficient of thermal expansion of - 12 to + 12 x 10<SP>-7</SP>/ C. (0-700 C.), wherein (a) the inner diameter of said passageways is at least 3 times the wall thickness through portions of said walls common to adjacent fused tubes and (b) the open fronted or cross-sectional area of each face of the matrix containing passageways is at least 32% of the cross-sectional area across such face. Such matrices can withstand temperatures of at least 1500 F. for at least 1000 hours and will have dimensional stability of less than 250 p.p.m. Further matrices may have a thermal conductivity at 400 C. of less than 0À01 cal./ cm./sec./cm.<SP>2</SP>/ C. and an open fronted crosssectional area of at least 60%. The cellular matrix may be made by packing sealed tubes parallel to the length of a mould lined with a layer of heat-resistant alumina-silica paper. The assembly is heated to produce a glassceramic matrix, in like manner to the above, the heat treatment fusion bonding the walls of each tube to those of adjacent tubes and reforming each tube to substantially hexagonal shape. Alternatively a plurality of layers of tubes are superimposed one above the other in successive parallel planes, the tubes within each plane being essentially parallel to each other and transverse to tubes in adjacent layers.